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Convergence of Theory and Experiment on the Role of Preorganization, Quantum Tunneling, and Enzyme Motions into Flavoenzyme-Catalyzed Hydride Transfer
dc.contributor.author | Delgado, Manuel | |
dc.contributor.author | Görlich, Stefan | |
dc.contributor.author | Scrutton, Nigel | |
dc.contributor.author | Hay, Sam | |
dc.contributor.author | Moliner, Vicent | |
dc.contributor.author | Tuñón, Iñaki | |
dc.date.accessioned | 2017-11-03T08:46:37Z | |
dc.date.available | 2017-11-03T08:46:37Z | |
dc.date.issued | 2017 | |
dc.identifier.citation | DELGADO, Manuel, et al. Convergence of Theory and Experiment on the Role of Preorganization, Quantum Tunneling, and Enzyme Motions into Flavoenzyme-Catalyzed Hydride Transfer. ACS Catalysis, 2017, vol. 7, no 5, p. 3190-3198. | ca_CA |
dc.identifier.issn | 2155-5435 | |
dc.identifier.uri | http://hdl.handle.net/10234/169821 | |
dc.description.abstract | Hydride transfer is one of the most common reactions catalyzed by enzymatic systems, and it has become an object of study because of possible significant quantum tunneling effects. In the present work, we provide a combination of theoretical QM/MM simulations and experimental measurements of the rate constants and kinetic isotopic effects (KIEs) for the hydride transfer reaction catalyzed by morphinone reductase, MR. Quantum mechanical tunneling coefficients, computed in the framework of variational transition-state theory, play a significant role in this reaction, reaching values of 23.8 ± 5.5 for the lightest isotopologue—one of the largest values reported for enzymatic systems. This prediction is supported by the agreement between the theoretically predicted rate constants and the corresponding experimental values. Simulations indicate that the role of protein motions can be satisfactorily described as equilibrium fluctuations along the reaction coordinate, in line with a high degree of preorganization displayed by this enzyme. | ca_CA |
dc.description.sponsorShip | V.M. is grateful to the University of Bath for the award of a David Parkin Visiting Professorship. The authors thankfully acknowledge the computer resources, technical expertise and assistance provided by the “Centre de Calcul de la Universitat de València” through the use of Multivac and Tirant. | |
dc.format.extent | 9 p. | ca_CA |
dc.format.mimetype | application/pdf | ca_CA |
dc.language.iso | eng | ca_CA |
dc.publisher | American Chemical Society | ca_CA |
dc.relation.isPartOf | ACS Catalysis, 2017, vol. 7, no 5 | |
dc.rights | Copyright © American Chemical Society | ca_CA |
dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | * |
dc.subject | hydride transfer | ca_CA |
dc.subject | kinetic isotope effects | ca_CA |
dc.subject | molecular dynamics | ca_CA |
dc.subject | morphinone reductase | ca_CA |
dc.subject | QM/MM | ca_CA |
dc.title | Convergence of Theory and Experiment on the Role of Preorganization, Quantum Tunneling, and Enzyme Motions into Flavoenzyme-Catalyzed Hydride Transfer | ca_CA |
dc.type | info:eu-repo/semantics/article | ca_CA |
dc.identifier.doi | http://dx.doi.org/10.1021/acscatal.7b00201 | |
dc.relation.projectID | Spanish Ministerio de Economia y Competitividad / CTQ2015-66223-C2); Universitat Jaume I / project P1·1B2014-26; Generalitat Valenciana / PROMETEOII/2014/022; U.K. Biotechnology and Biological Sciences Research Council / BBSRC; BB/ M007065/1 and BB/H021523/1); N.S.S is an Engineering and Physical Sciences Research Council (EPSRC) Established Career Research Fellow / EP/J020192/1 | ca_CA |
dc.rights.accessRights | info:eu-repo/semantics/restrictedAccess | ca_CA |
dc.relation.publisherVersion | http://pubs.acs.org/doi/abs/10.1021/acscatal.7b00201 | |
dc.type.version | info:eu-repo/semantics/publishedVersion | ca_CA |
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